JP2017045062A - Low refractive index diffuser element having interconnected voids - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide low refractive index diffuser layers that include haze generating particles dispersed in smaller porous particles.SOLUTION: An optical diffuser layer comprises: a binder; a plurality of metal oxide particles dispersed in the binder; a plurality of interconnected voids; and a plurality of haze generating particles dispersed in the binder. The optical diffuser layer has an effective refractive index of 1.3 or less.SELECTED DRAWING: Figure 2

Description

  Articles having nanometer sized pores or void structures may be useful in a variety of applications based on the optical, physical, or mechanical properties provided by these nanohollow compositions. For example, a nanohollow article includes a solid network or matrix of polymer that at least partially surrounds pores or voids. The pores or voids are often filled with a gas such as air. The size of the pores or voids in the nanohollow article can be described as having an average effective diameter, which can generally range from about 1 nanometer to about 1000 nanometers. The International Union of Pure and Applied Chemistry (IUPAC) is a nanopore with three dimensions: micropores with voids less than 2 nm, mesopores with voids between 2 nm and 50 nm, and macropores with voids greater than 50 nm. The category of pore material was defined. Each of the different size categories can provide unique properties to the nanohollow article.

  For example, using several techniques, including polymerization induced phase separation (PIPS), thermally induced phase separation (TIPS), solvent induced phase separation (SIPS) emulsion polymerization, and foaming / blowing agent addition polymerization, Or void-containing articles were produced. In many cases, porous or hollow articles produced by these methods require a cleaning step to remove the materials used to form the construct, such as surfactants, oils, or chemical residues. The cleaning process can limit the size range and uniformity of the pores or voids formed. The types of materials that can be used with these techniques are also limited.

  The present disclosure relates to low index diffuser layers. In particular, the present disclosure relates to a low refractive index diffuser layer comprising haze generating particles dispersed in smaller porous particles.

  In one exemplary embodiment, the optical diffuser includes a binder, a plurality of metal oxide particles dispersed in the binder, and a plurality of interconnected voids. The plurality of haze generating particles are dispersed in the binder. The optical diffuser layer has an effective refractive index of 1.3 or less.

  In another exemplary embodiment, the optical article includes an optical element and an optical diffuser layer disposed on the optical element. The optical diffuser layer comprises a binder, a plurality of metal oxide particles dispersed in the binder, a plurality of interconnected voids, and a plurality of haze-generating particles dispersed in the binder. Including. The optical diffuser layer has an effective refractive index of 1.3 or less.

  In a further exemplary embodiment, the optical article includes an optical element, a low refractive index layer disposed on the optical element, and a second low refractive index disposed on the optical element or low refractive index layer. Including layers. The low refractive index layer includes a binder, a plurality of first metal oxide particles having a first average lateral dimension and a plurality of interconnected voids dispersed in the binder, and in the binder And a plurality of haze-generating particles dispersed in. The low refractive index layer has an effective refractive index of 1.3 or less. The second low refractive index layer includes a binder, a plurality of metal oxide particles dispersed in the binder, and a plurality of interconnected voids. The second low refractive index layer has an effective refractive index of 1.3 or less.

  These mechanisms and advantages, as well as various other mechanisms and advantages, will become apparent upon reading the following Detailed Description.

A more complete understanding of the present disclosure can be obtained by considering the following detailed description of different embodiments of the disclosure in conjunction with the accompanying drawings.
1 is a schematic side view of an exemplary optical article. FIG. FIG. 3 is a schematic side view of another exemplary optical article.

  The scale of the drawings is not necessarily accurate. Like numbers used in the drawings shall refer to like components. It will be understood, however, that the use of a number to indicate an element in a particular figure does not limit that element in another figure indicated by the same number.

  In the following description, reference is made to a series of accompanying drawings that form a part hereof, and in which are shown by way of illustration several specific embodiments. It should be understood that other embodiments may be envisaged and practiced without departing from the scope and spirit of the present disclosure. The following detailed description is, therefore, not to be construed in a limiting sense.

  Unless otherwise indicated, all numbers representing the size, quantity, and physical properties of features used in the specification and claims are understood to be modified in any case by the term “about”. Should be. Therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and the appended claims are not intended to be targeted by those skilled in the art using the teachings disclosed herein. It is an approximate value that can vary depending on the characteristics of

  As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include embodiments unless the context clearly dictates otherwise. Is included. As used herein and in the appended claims, the term “or” is generally employed in its sense including “and / or” unless the content clearly dictates otherwise.

  Spatial terms such as, but not limited to, “lower”, “upper”, “lower”, “lower”, “upper”, and “upper” are used herein. Is used for ease of explanation in describing the spatial relationship of one element to another. Such spatially related terms include different orientations of the device in use or in operation other than the particular orientation shown in the figures and described herein. For example, if the cell shown in the figure is flipped or flipped, the portion previously described as below or below other elements will be above these other elements.

  As used herein, an element, member or layer is “on”, “connected to” these, for example to form a “coincident interface” with another element, member or layer. ”,“ Coupled ”or“ contacting ”, the element, member or layer is, for example, directly on or directly connected to a particular element, member or layer, May be directly coupled or in direct contact, or intervening elements, members or layers may be on, connected to, coupled to, or in contact with particular elements, members or layers . For example, an element, member or layer is represented by an expression beginning with “directly on” another element, “directly connected”, “directly coupled” or “directly contacted” with another element. There are no intervening elements, members or layers.

  The present disclosure relates to low index diffuser layers. In particular, the present disclosure relates to a low refractive index diffuser layer comprising haze generating particles dispersed in smaller porous particles. The present disclosure describes film-structured integrated optics that can be useful for display applications. In particular, the present disclosure describes a low refractive index layer that is haze and can function as a diffuser sheet. The present disclosure reduces the number of individual optical elements or films required in display applications. While the present disclosure is not so limited, a description of the examples provided below will provide recognition of various aspects of the present disclosure.

Some embodiments of the diffuser coating, article or construct of the present disclosure include one or more low refractive index layers comprising a plurality of voids dispersed in a binder. This void has a refractive index n _v and a dielectric constant ε _v . Here, n _v ² = ε _v and the binder has a refractive index n _b and a dielectric constant ε _b , where n _b ² = ε _b . In general, the interaction between a low refractive index layer and light, such as light incident on the low refractive index layer or light propagating through the low refractive index layer, may include, for example, film or layer thickness, binder refractive index, voids or It depends on the properties of a number of films or layers, such as the refractive index of the pores, the pore shape and dimensions, the spatial distribution of the pores, and the wavelength of light. In some embodiments, light incident on or propagating through the low index layer “witnesses” or “experiences” the effective dielectric constant ε _eff and the effective index n _eff . _Where n _eff can be expressed in the form of void refractive index n _v , binder refractive index n _b , and void porosity or volume fraction “f”. In such embodiments, the low refractive index layer is thick enough and the voids are small enough that light cannot resolve the shape and characteristics of a single or isolated void. In such embodiments, at least a majority of the voids, for example, at least 60%, or 70%, or 80%, or 90% of the voids have a dimension of about λ / 5 or less, or about λ / 6 or less, or about λ / 8 or less, or about λ / 10 or less, or about λ / 20 or less, where λ is the wavelength of light. In some embodiments, some voids can be small enough so that their primary optical effect lowers the effective refractive index, and some other voids reduce the effective refractive index, Light can be scattered, and some other voids can be large enough so that their primary optical effect scatters the light.

  In some embodiments, the light incident on the low refractive index layer is visible light, meaning that the wavelength of the light is in the visible region of the electromagnetic spectrum. In these embodiments, the visible light has a wavelength in the range of about 380 nm to about 750 nm, or about 400 nm to about 700 nm, or about 420 nm to about 680 nm. In these embodiments, the dimension of at least the majority of the voids, such as at least 60%, 70%, 80%, or 90% of the voids, is about 70 nm or less, about 60 nm or less, about 50 nm or less, about 40 nm or less. , About 30 nm or less, about 20 nm or less, or about 10 nm or less, the low refractive index layer has an effective refractive index and includes a plurality of voids.

  In some embodiments, the low refractive index layer is sufficient so that the low refractive index layer has an effective refractive index that can be expressed in terms of the refractive index of the voids and binder, and the volume fraction or porosity of the voids or pores. Thick. In such embodiments, the low refractive index layer thickness ranges from about 1 micrometer or more, or from about 2 micrometers or more, or from 1 to 20 micrometers.

When the voids in the disclosed low refractive index layer are small enough and the low refractive index layer is thick enough, the low refractive index layer is ε _eff
It has an effective dielectric constant ε _eff that can be expressed as ε _eff = fε _v + (1−f) ε _b (1).

In these embodiments, the effective refractive index n _eff of the optical film or low refractive index layer is:
n _eff ² = fn _v ² + (1−f) n _b ² (2).

In some embodiments, such as when the difference between the refractive index of the pores and the binder is sufficiently small, the effective refractive index of the low refractive index layer can be approximated by the following equation:
n _eff = fn _v + (1−f) n _b (3)
In these embodiments, the effective refractive index of the low refractive index layer is a volume weighted average of the refractive indices of the voids and the binder. Under ambient conditions, this void contains air, so the refractive index n _v for this void is approximately 1.00. For example, an optical film or low refractive index layer with a void volume fraction of about 50% and a binder with a refractive index of about 1.5 has an effective refractive index of about 1.25.

  In some embodiments, the effective refractive index of the low refractive index layer is not greater than (ie, less than) about 1.3, or less than about 1.25, or less than about 1.2, or about 1. Less than 15, or less than about 1.1. In some embodiments, the refractive index is from about 1.14 to about 1.30. In some embodiments, the low refractive index layer comprises a binder, a plurality of particles, and a plurality of interconnected voids or a network of interconnected voids. In other embodiments, the low refractive index layer comprises a binder, a plurality of particles, and a plurality of interconnected voids or a network of interconnected voids.

  A plurality of interconnected voids or a network of interconnected voids can occur in a number of ways. In one method, the inherent porosity of highly structured, high surface area fumed metal oxides such as fumed silica oxide is used in a mixture of binders to crosslink binders, particles, voids and optionally crosslinks. A composite structure is formed in which agents or other auxiliary materials are integrated. The desired binder to particle ratio depends on the type of method used to form the interconnected voided structure.

  Binder resins are not a prerequisite for the formation of porous fumed silica structures, but typically a shaped polymer resin or binder is incorporated into the metal oxide network to make the final structure workable, coating quality It is desirable to improve adhesion and durability. Examples of useful binder resins are those derived from thermosetting, thermoplastic, and UV curable polymers. Examples include polyvinyl alcohol, (PVA), polyvinyl butyral (PVB), polyvinyl pyrrolidone (PVP), polyethylene vinyl acetate copolymer (EVA), cellulose acetate butyrate (CAB) polyurethane (PUR), polymethyl methacrylate (PMMA), Examples include polyacrylates, epoxies, silicones, and fluoropolymers. The binder can be soluble in a suitable solvent such as water, ethyl acetate, acetone, 2-butone, or can be used as a dispersion or emulsion. Examples of some commercially available binders useful in this mixture are those available from Kuraray-USA, Wacker Chemical, Dyneon LLC, and Rohm and Haas. The binder can be a polymer system, but it can also be added as a polymerizable monomer system such as UV or a thermoset or cross-linked system. Examples of such systems are UV polymerizable acrylates, methacrylates, multifunctional acrylates, urethane acrylates, and mixtures thereof. Some typical examples are 1,6 hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate. Such systems are readily available from suppliers such as Neo Res (Newark, DE), Arkema (Philadelphia, PA), or Sartomer (Exton, PA). Actinic radiation, such as electron (E), gamma and ultraviolet (UV) radiation, is a useful method for initiating polymerization of these systems, and many embodiments use UV active systems. Other useful binder systems are also cationically polymerizable and such systems are available as vinyl ethers and epoxides.

  The polymeric binder can also be formulated with a crosslinking agent that can be chemically bonded to the polymeric binder to form a crosslinked network. The formation of crosslinks is not a prerequisite for the formation of porous structures or low refractive index optical properties, but such as improved cohesive strength of coatings, adhesion to substrates or water resistance, or improved heat and solvent resistance. Often desirable for other functionality reasons. The specific type of crosslinking agent depends on the binder used. Typical crosslinkers for polymer binders such as PVA are diisocyanates, titanates such as TYZOR-LA ™ (available from DuPont (Wilmington, DE), PolyCup 172 (available from Hercules, Wilmington, DE). Poly (epichlorohydrin) amide adducts such as CX100 (available from Neo-Res (Newark, DE)) and boric acids, diepoxides, diacids and the like.

  The polymer binder may form a separate phase with the particle agglomerates or bind the agglomerates together to form ionic, dipolar, van der Waals forces, hydrogen bonds and physical bonds with the metal oxide. The particles may be interdispersed by a method of forming a structure connected to metal oxide particles by direct covalent bond formation such as entanglement or molecular interaction.

  Exemplary particles include, for example, fumed metal oxides such as fumed silica or alumina or ignited metal oxides. In some embodiments, highly branched or structured particles may be used. Such particles prevent efficient packing in the binder matrix and form interstitial voids or pores. Typical materials comprising highly branched or structured particles include Cabo-Sil ™ fumed silica, or fumed silica or silica dispersions sold under the trade name EH5, TS 520, for example. Or available as Cabo-Sperse ™ PG 001, PG 002, PG 022, 1020K, 4012K, 1015A (available from Cabot Corporation (Bellerica, Mass.)), And Aerodisp® W7622, Aerodisp ( Pre-dispersed H such as those available from Evonik-USA (Parsippany, NJ) such as W7612S®, Aerodisp® W7615S, and Aerodisp® W630. Mudoshirika particles, and the like. Silica may be preferred because it has an inherently low skeletal refractive index than alumina, but fumed aluminum oxide is also a structured particle useful for the formation of a low refractive index system. Examples of aluminum oxides are available under the trade name Cabo-Sperse, such as those sold under the trade name Carbo-Sperse ™ PG003 or CabotSpec-Al ™. In some embodiments, these representative fumed metal oxide agglomerates comprise a plurality of primary particles in the range of about 8 nm to about 20 nm, and a broad distribution in the size range of about 80 nm to greater than 300 nm. To form a highly branched structure. In some embodiments, these agglomerates are randomly packed into a unit volume of the coating to form a mesoporous structure having a complex bicontinuous network of channels, tunnels, and pores. These trap air in the network, thus reducing the density and refractive index of the coating. Other useful porous materials are derived from naturally derived inorganic materials such as clay, barium sulfate, aluminum silicate and the like. When the metal oxide is silica oxide, the low refractive index layer has an effective refractive index of 1.23 or less, and when the metal oxide is alumina oxide, the effective refractive index of 1.33 or less. Have

  Fumed silica particles can also be treated with a surface treatment agent. The surface treatment of the metal oxide particles can provide, for example, improved dispersion in the polymer binder, modified surface properties, enhanced particle-binder interaction, and / or reactivity. In some embodiments, the surface treatment stabilizes the particles such that the particles are well dispersed in the binder, resulting in a substantially more homogeneous composition. The incorporation of surface-modified inorganic particles can be adjusted, for example, to enhance the covalent bonding of the particles to the binder, resulting in a more durable and more homogeneous polymer / particle network.

  The preferred type of treating agent is determined in part by the chemical nature of the metal oxide surface. Silane is preferred for silica and other siliceous fillers. In the case of silane, it may be preferable to react the silane with the particulate diisocyanate surface prior to incorporation into the binder. The required amount of surface modifier depends on several factors such as, for example, particle size, particle type, modifier molecular weight, and / or modifier type. The diisocyanate silane modifier has a reactive group that forms a covalent bond between the particle and the diisocyanate binder, such as carboxy, diisocyanate alcohol, diisocyanate isocyanate, diisocyanate acryloxy, diisocyanate epoxy, diisocyanate thiol or diisocyanate amine. be able to. Conversely, the silane modifier can have non-reactive groups such as alkyl, alkoxy, phenyl, phenyloxy, polyether, or mixtures thereof. For example, such non-reactive groups may modify the surface of the coating in order to improve soil resistance or static dissipation. Commercially available examples of surface modified silica particles include, for example, Cabo-Sil ™ TS 720 and TS 530. It may sometimes be desirable to incorporate a mixture of functional and non-functional groups on the surface of the particle to obtain a combination of these desired features.

  Representative embodiments of surface treating agents suitable for use in the compositions of the present disclosure include, for example, N- (3-triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate, N- (3-triethoxysilylpropyl) ) Methoxyethoxyethoxyethyl carbamate, 3- (methacryloyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloyloxy) propylmethyldimethoxysilane, 3 -(Acryloyloxypropyl) methyldimethoxysilane, 3- (methacryloyloxy) propyldimethylethoxysilane, 3- (methacryloyloxy) propyldimethylethoxysilane, vinyldimethylethoxysilane, Nyltrimethoxysilane, n-octyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyl Triethoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-t-butoxysilane, vinyltris-isobutoxysilane, vinyltriisopropenoxysilane, vinyltris (2-methoxyethoxy) silane, styryl Ethyltrimethoxysilane, mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, acrylic acid, methacrylic acid, oleic acid Acid, stearic acid, dodecanoic acid, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid (MEEAA), β-carboxyethyl acrylate (BCEA), 2- (2-methoxyethoxy) acetic acid, methoxyphenylacetic acid, And combinations thereof.

Particle volume concentration (PVC) and critical particle volume concentration (CPVC) can be used to characterize the porosity of the particle binder system used in making the coating. The terms PVC and CPVC are well-defined terms in the paint and pigment literature, and are frequently referenced articles and, for example, “Paint Flow and Pigment Distribution” (Patton, TC, 2nd Edition, J. ^MoI . Wiley Interscience, 1978, Chapter 5, p. 126) and “Modeling Cluster Voices and Pigment Distribution to Predict Properties and CPVC in Coatings. Part 1: Dry Coating Ath. D; further defined in technical texts such as “Pigment and Resin Technology, 2008” (37 (6) .p.375).

  If the volume concentration of the particles is greater than CPVC, the coating is porous because there is not enough binder to fill all the gaps between the particles and interstitial areas of the coating. The coating then becomes a mixture of binder, particles, and voids. The volume concentration at which this occurs is related to particle size and particle structure wetting and / or shape. Formulations having volume concentrations above CPVC have resin volume defects in the mixture that are displaced by air. The relationship between CPVC, PVC and porosity is:

  Materials that provide the desired low refractive index properties have highly structured submicron pores derived from the particle / binder mixture and are formulated at or above its CPVC. In some embodiments, the optical article has a CPVC value that is not greater than (or less than) about 60%, or less than about 50%, or less than about 40%.

  As described above, highly branched or structured particles prevent efficient packing in the binder matrix and form interstitial voids or pores. In contrast, the material combination that breaks the desired CPVC is not sufficiently porous. Since the BET method analyzes pores with a diameter of less than 200 nm, a diameter of less than 100 nm, or even less than 10 nm, it may be useful in determining the porosity of CPVC and thus low refractive index materials. As used herein, the term “BET method” refers to Braunauer, Emmett, and Teller surface area analysis (S. Brunauer, PH Emmett and E. Teller, J. Am. Chem. Soc., 1938). , 60, 309). The BET method is a well-known scientifically validated method used to quantify the pore size, surface area, and percent porosity of solid materials. BET theory relates to the physical adsorption of gas molecules on a solid surface and serves as a basis for obtaining physical information about the surface area and porosity of the solid surface. BET data can assist in characterizing materials that meet the minimum requirements to form a porous structure.

  The volume concentration of the particles described by the PVC / CPVC relationship is also related to the weight concentration of the particles. It is therefore possible to establish a weight range of particles that is greater than or equal to CPVC. The use of a weight ratio or weight percent is one way to formulate a mixture of desired CPVC values. A binder: particle weight ratio of 1: 1 to 1: 8 is desirable for the optical construction of the present disclosure. A weight ratio of 1: 1 is equivalent to about 50 wt% particles, and 1: 8 is equivalent to about 89 wt% particles. Typical binder to metal oxide particle ratios are less than 1: 2 (less than 33% binder), less than 1: 3, less than 1: 4, less than 1: 5, less than 1: 6, 1: 7. Less than 1: 8, less than 1: 9, and less than 1:10 (about 8-10% binder). The upper limit of the binder may be determined by the desired refractive index. The lower limit of the binder may be determined by the desired physical properties, such as processability or ultimate durability. Thus, the binder: particle ratio varies depending on the desired end use and desired optical article properties.

  In general, the low refractive index layer can have any porosity, pore size distribution, or void volume fraction that may be desired in the application. In some embodiments, the volume fraction of the plurality of voids in the low refractive index layer is about 20% or more, or about 30% or more, or about 40% or more, or about 50% or more, or about 60% or more. Or about 70% or more, or about 80% or more.

In some embodiments, even if the low refractive index layer has high optical haze and / or diffuse reflection, a portion of the low refractive index layer may exhibit some low refractive index properties. For example, in such embodiments, a portion of the low refractive index layer may support the optical gain at the angle corresponding to a smaller refractive index than the refractive index n _b of the binder.

  In some embodiments, some of the particles have reactive groups and other particles do not have reactive groups. For example, in some embodiments, about 10% of the particles have reactive groups, about 90% of the particles have no reactive groups, or about 15% of the particles have reactive groups; About 85% of the particles have no reactive groups, or about 20% of the particles have reactive groups, about 80% of the particles have no reactive groups, or about 25% of the particles are reactive. About 75% of the particles have no reactive groups, or about 30% of the particles have reactive groups, and about 60% of the particles have no reactive groups, or about 35% of the particles have reactive groups, about 65% of the particles have no reactive groups, or about 40% of the particles have reactive groups, and about 60% of the particles have reactive groups. Or about 45% of the particles have reactive groups, about 55% of the particles have no reactive groups, or about 50% of the particles have reactive groups and about 50% The particles do not have reactive groups. In some embodiments, some particles may be functionalized with both reactive and non-reactive groups on the same particle.

  Particle aggregates can be sized, particles having reactive and non-reactive groups, and organic particles including different types of particles, for example polymer particles such as acrylic, polycarbonate, polystyrene, silicone, etc., or for example silica and It may also contain a mixture of inorganic particles such as glass or ceramics such as zirconium oxide.

In some embodiments, the low index layer or material is greater than about 30% BET porosity (corresponding to a surface area of about 50 m ² / g as measured by the BET method), greater than about 50% ( about 65~70m corresponds to the surface area of the ² / g) porosity as measured by the BET method, is about 60 percent (corresponding to a surface area of approximately 80~90m ² / g as measured by BET method) porous , And most preferably between about 65% and about 80% (corresponding to a slightly higher surface area of about 100 m ² / g as measured by the BET method). In some embodiments, the volume fraction of the plurality of interconnected voids in the low refractive index layer is greater than or equal to about 20% (ie greater than about 20%), or greater than about 30%, or about 40 %, Or more than about 50%, or more than about 60%, or more than about 70%, or more than about 90%. In general, it can be shown that the greater the surface area, the greater the percent porosity and therefore the lower the refractive index, but the relationship between these parameters is complex. The values shown in this disclosure are for guidance purposes only and are not intended to illustrate the limited correlation between these properties. The BET surface area and percent porosity values are determined by the need to balance other critical performance such as low refractive index and coating cohesion.

  The optical structures of the present disclosure can have any desired optical haze. In some embodiments, the low index layer is at least about 20% (or greater than about 20%), or greater than about 30%, or greater than about 40%, or greater than about 50%, or greater than about 60%. Or an optical haze that is greater than about 70%, or greater than about 80%, or greater than about 90%, or greater than about 95%.

  In some embodiments, portions of adjacent major surfaces of each two adjacent layers of the optical construction are in physical contact with each other. For example, some of the adjacent major surfaces of each adjacent layer of the optical structure are in physical contact with each other. For example, at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95% of two adjacent major surfaces Make physical contact.

  In some embodiments, portions of adjacent major surfaces (major surfaces that face each other or are adjacent to each other) of each of the two adjacent layers in the optical construction are in physical contact with each other. For example, in some embodiments, although not explicitly shown in the figure, there may be one or more additional layers disposed between the low index layer and the optical element. In such embodiments, a substantial portion of adjacent major surfaces of each two adjacent layers in the optical construction are in physical contact with each other. In such embodiments, at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80 of the adjacent major surface of each two adjacent layers in the optical construction. %, Or at least 90%, or at least 95% are in physical contact with each other.

  There are a number of coating techniques known in the art that are useful for making the embodiments described herein. More general techniques are well known roll-to-roll automation methods such as, but not limited to, knife bars, slot dies, slides, curtains, rolls, and gravure coating techniques. It is also possible to coat these solutions using non-continuous methods such as ink jet, screen, offset printing, dip and spray coating techniques. Strict coating techniques are not important for obtaining low refractive index properties, but some techniques allow multiple layers to be coated simultaneously on a substrate, which can improve the economics of the coating process. it can. The desired end use determines which technique is preferred.

  FIG. 1 is a schematic side view of an exemplary optical article 10. The optical article 10 includes an optical diffuser layer 30 that includes a binder, a plurality of metal oxide particles dispersed in the binder, and a plurality of interconnected voids. The plurality of haze generating particles 60 are dispersed in the binder. The optical diffuser layer 30 has an effective refractive index of 1.3 or less, or 1.23 or less, or 1.2 or less. An optical diffuser layer 30 can be disposed on the optical element 20 to form the optical article 10.

  The haze generating particles 60 can be any useful particle such as, for example, polystyrene particles. Haze generating particles 60 can have any useful diameter or average lateral dimension of 0.5 to 5 micrometers, 1 to 10 micrometers, or such as 1 micrometer or more. In some embodiments, the plurality of haze-generating particles 60 have an average lateral dimension in the range of 1-10 micrometers, and the plurality of metal oxide particles has an average lateral dimension in the range of 500 nanometers or less. Have

  The optical diffuser layer 30 can have any useful haze and transparency value. In many embodiments, the optical diffuser layer 30 has a haze value of at least 40%, or at least 60%, or at least 80%. In many embodiments, the optical diffuser layer 30 has a transparency value of less than 50%, or less than 25%, or less than 15%. The optical diffuser layer 30 can have any useful thickness. In many embodiments, the optical diffuser layer 30 has a thickness in the range of 1-20 micrometers.

  The optical element 20 can have any useful optical element. In some embodiments, the optical element 20 is a polarizing film, a diffusing film, a reflective film, a retardation film, a light guide, or a liquid crystal display panel. In some embodiments, the optical element 20 is a substrate that is transparent or transmissive to visible light. In some embodiments, the optical element 20 can be an absorptive polarizer or a reflective polarizer. Examples of the reflective polarizing plate include fiber, multilayer, cholesteric, and wire grid reflective polarizing plates. Examples of the multilayer reflective polarizing plate include a brightness enhancement film (BEF) and a dual brightness enhancement film (DBEF) commercially available from 3M Company (St. Paul, MN). In some embodiments, the optical element 20 is a light retroreflective film and can be diffractive and / or refractive. In some embodiments, the optical element 20 can be a graphic film, cellulose triacetate, or an optical adhesive.

  FIG. 2 is a schematic side view of another exemplary optical article 50. The optical article 50 includes an optical element 20, a low refractive index layer 30 disposed on the optical element 20, and a second low refractive index layer 40 disposed on the optical element 20 or the low refractive index layer 30. And including. FIG. 2 illustrates a second low refractive index layer 40 disposed on the low refractive index layer 30, but the second low refractive index layer 40 is between the optical element 20 and the low refractive index layer 30. It is understood that the optical element 20 can be between the two low refractive index layers 30 and 40.

  The low index layer 30 is described above and includes a binder, a plurality of first metal oxide particles having a first average lateral dimension dispersed in the binder, a plurality of interconnected voids, and A plurality of haze generating particles 60 dispersed in a binder. The low refractive index layer 30 has an effective refractive index of 1.3 or less. The second low refractive index layer 40 includes a plurality of second metal oxide particles having a second average lateral dimension different from the first average lateral dimension, dispersed in the binder, and a plurality of second metal oxide particles. Interconnected air gaps. The second low refractive index layer 40 has an effective refractive index of 1.3 or less. The optical article 50 can have an effective refractive index of 1.3 or less, or 1.23 or less, or 1.2 or less.

  In some embodiments, the first low refractive index layer 30 has a high haze value (e.g., at least 50%, or at least 60%, or at least 75%, or at least 90%) and the second low refractive index layer 30. The refractive index layer 40, the low refractive index layer 30 disposed on the optical element 20, and the second low refractive index layer 40 have a low haze (eg, less than 20% or less than 10%).

  In some embodiments, the optical adhesive bonds the optical article 10, 50 to a second optical article (not shown). The second optical element can be any useful optical element. In some embodiments, the optical element is a polarizing film, a diffusing film, a reflective film, a retardation film, a light guide or a liquid crystal display panel. In some embodiments, the second optical element is a substrate that is transparent or transmissive to visible light.

A comparative coating solution CE-1 was made from a mixture of polyvinyl alcohol, Kuraray PVA-235 and fumed silica oxide dispersion Cab-O-Sperse ™ 1020K. PVA is (88% hydrolyzed medium molecular weight polyvinyl alcohol available from Kuraray-USA (Houston, TX)). Cab-O-Sperse ™ 1020K is a non-surface-decorated, alkali-stabilized silica dispersion of L90 fumed silica, available from Cabot Corporation (Billerica, Mass.). In a typical method, 138.8 g of 7.2 wt% PVA 235 solution is loaded into an 800 ml plastic beaker (10.0 g PVA 235 on a dry weight basis) followed by 2.0 g of 10 wt% Tergitol Min-Foam 1X. And 1 ml of concentrated NH ₄ OH solution was added. Tergitol ™ Min-Foam 1X is a non-ionic surfactant available from Dow Chemical (Midland, MI). These ingredients were mixed thoroughly with a stir bar, followed by the addition of 200 g Cab-O-Sperse ™ 1020K, 20 wt% fumed silica in water and an additional 162 g deionized (DI) water. This component was mixed well using an air driven mixer at low shear to reduce foaming. After mixing for about 5 minutes, the contents are transferred to a 1 L one-necked round bottom flask and available as Rotovap ™ from the rotary evaporator system (Buchi GmbH (Flawil, Switzerland) at 40 ° C. and 600 mm Hg (80.0 kPa) vacuum. ) To degas the mixture. The final mixture for CE-1 consisted of 1 part PVA resin: 4 parts silica (1: 4 PVA-Si ratio, 20 wt% PVA) on a dry weight basis. The pH of the final solution was typically between 9.2 and 10.2. The final solid content was adjusted to between 9.5 and 10.5% wt.

  Preparation of low refractive index diffuser coating solution (EX-1) using polystyrene beads: 504 g of 9.6 g Soken KSR 3 cross-linked polystyrene beads prepared as described in CE-1 (1-4 PVA-Si 1020K). A coating solution EX-1 was prepared by adding a 10% solids low refractive index mixture. KSR 3A is a product of Soken Chemical and Engineering Co. Ltd .. (Sayama-Shi, Saitama-Ken Japan). KSR 3A beads were incorporated into the low refractive index coating solution using an air driven mixer at low shear to reduce foaming. The final mixture was transferred to a 1 L one neck round bottom flask and the mixture was degassed on a Rotovap at 40 ° C. and 600 mm Hg (80.0 kPa) vacuum. The final solids of the ULI-diffuser coating mixture was 11.7% and consisted of 16.8 wt% PVA, 67.2 wt% 1020K silica and 16 wt% KSR 3 polystyrene beads on a dry weight basis.

  Preparation of surface-modified silica particles with 50% A174 and 50% isooctyltrimethoxysilane used in coating solutions CE-2 and EX-2 and EX-3: stir bar, stir plate, condenser, heating mantle and thermocouple / A 1000 ml three-necked flask equipped with a temperature controller was charged with 400 g of Cab-O-Sperse ™ PG002 (available from Cabot Corp (Boston, Mass.)) Fumed silica 20 wt% solids dispersion. 50 g of isopropanol was added to the dispersion while mixing. Next, 6.15 g of 3- (methacryloxypropyl) trimethoxysilane (A-174, Alfa Aesar (available as Ward Hill, MA as Stock # A17714), 5.80 g of isooctyltrimethoxysilane (Gelest, Inc. (available from Morrisville, PA as stock # SII6458.0) and 50 g of a premix of isopropanol were added with mixing, and the premix beaker was rinsed with an aliquot of isopropanol totaling 50 g. Isopropanol was added to the batch, and the resulting mixture was a haze, translucent dispersion, which was heated to 50 ° C. and held for approximately 30 minutes, after 30 minutes at 50 ° C. Is a homogeneous, opaque white At this point 250 g of isopropanol was added to the batch and the batch was heated to reflux (˜80 ° C.) and held with mixing. An additional 200 g of isopropanol was added, the batch became much less viscous, and the batch was held at reflux for a total of 6 hours After 6 hours at reflux, the batch was cooled to room temperature with mixing. At this point, the batch was a thick off-white slurry and some dry solid had adhered to the walls of the reaction flask.The resulting reaction mixture was replaced with an alternative vacuum distillation and 1200 g of 1-methoxy-2. The solvent was changed to 1-methoxy-2-propanol by addition of -propanol The batch was further concentrated by vacuum distillation. It was a translucent dispersion with a high viscosity of 5.4 wt% solids.

  Coating solution CE-2 was made at a silica to resin weight ratio of 1-4 using the surface modified PG 002 silica described above and UV curable urethane acrylate oligomer CN 9013 available from Sartomer USA (Exton, PA). 50 g of modified PG 002 (15.4% solids, 7.7 g solids) was mixed with 1.28 g CN 9013 in an appropriately sized mixing vessel. 0.18 g of photoinitiator Irgacure 184 (available from Ciba USA (W. Paterson, NJ)) was added and the final mixture was diluted with an additional 12.5 g of 2-butanone to give 14.4% solids A final coating solution was obtained.

  Coating solutions EX-2 and EX-3 were made by mixing 100 g of coating solution CE-3 with silica powder matting agent EXP-3600 (available from Evoniks USA, Hopewell, Va.). The matting agent was dispersed by adding this powder to coating solution CE-3 followed by 2-butanone to adjust the final solids to 14%. This mixture contained 30 wt% silica or 50 wt% silica matting agent EXP 3600 on a dry weight basis for EX-2 and EX-3, respectively.

  Preparation of low refractive index diffuser coating solution with polystyrene beads for use in preparation of CE-3, EX-4-5: 1-6 weight PVA against PG003 (fumed alumina, available from Cabot Corp) Using the mixture, coating solutions CE-3 and EX-4-5 were prepared. Diffuser beads were added at 0%, 50%, and 70 wt%, respectively, to form low refractive index diffuser coatings CE-3 and EX-4-5. In these coatings, the beads used were Soken SX 350H, 3 μm cross-linked polystyrene beads with a narrower size distribution than specified for KSR-3A. Bead dispersion was improved by using a single stage rotor-stator mixer standard laboratory Ross Mixer rotating at 4000 rpm for 5 minutes, such as PreMax ™, available from Charles Ross & Son Company (Huppauge, NY).

Preparation of _PVA-Al 2 _{O 3} Premix -A: In a typical method, _(Al 2 _O 3 of 215 g) of 538g in 4L plastic beaker equipped with an air-driven mixer PG003, 10% of 25 g Tergitol (TM) Min-Foaam 1X surfactant and 542 g of PVA 235 (6.6% solids, 35.8 g) were charged. This mixture was stirred at low speed to homogenize all ingredients. After several minutes, 1405 g DI water was added and mixed gently to make Premix A containing 1-6 PVA-Al ₂ O ₃ at 10% solids. Comparative Example CE-3 was prepared using this coating solution.

  Preparation of diffuser bead premix-B: Mix 1440 g water, 16 g 10% Tergitol ™ Min-Foam 1X surfactant and 160 g SX-350H polystyrene beads in a 2 L plastic beaker equipped as described above. Thus, a homogeneous 10 wt% dispersion of Premix B was formed.

  Coating solution EX-4 was made by mixing 250 g of Premix A and 250 g of Premix B, followed by enhancing bead dispersion through a high shear dispersion process. This produced a mixture containing 50 wt% SX-350H diffuser beads.

  Coating solution EX-5 was made by mixing 150 g of Premix A and 350 g of Premix B, followed by enhancing bead dispersion through a high shear dispersion process. This produced a mixture containing 70 wt% SX-350H diffuser beads.

  Coating Method: All coatings were made using 50 micron primer treated PET film (Dupont-Teijin 689). By coating a low refractive index coating solution onto a primed polyester film, a small optically lab scale hand-painted coating with good optical quality was made. 14 × 11 in. Available from Elmeter Inc. (Rochester Hills, MI). The film was held flat by using a horizontal vacuum table model 4900 (35.6 cm x 27.9 cm). The coating solution was evenly spread on the PET using a wound coating rod (Meyer rod) available from RD Specialties (Webster, NY) or a knife bar available from Elcometer Inc (Rochester Hills, MI). In a typical procedure, a standard sheet of white paper (8.5 × 11 in (21.6 × 27.9 cm)) was placed between the vacuum table and the optical film to prevent coating defects associated with the vacuum table. . Using the degassed solution, all coatings were made avoiding optical defects such as air bubbles and surface cracks. A 5-8 mL sample of the coating solution is placed near the top of the film, and a 45 or 30 Meyer rod is used to make the coating, nominal wetting of 114 or 76.2 μm (4.5 or 3.0 mil), respectively. When a thick coating was obtained. When using a knife bar coater, coatings with a nominal wet thickness of 25.4 to 50.8 μm (1 to 2 mil), respectively, were obtained with a knife bar gap of 50.8 to 101.6 μm (2 to 4 mil). . The wet coating was air dried at room temperature for about 2-3 minutes, then carefully transferred to a flat glass plate and placed in a forced air oven at 50 ° C. to dry completely. The coating was covered with an appropriately sized aluminum pan to reduce the drying pattern on the film due to air movement in the oven.

  Coatings based on UV-curable urethane acrylate resin systems CE-2, EX-2 and EX-3 are coated using a # 30 Meyer rod to achieve a wet coating thickness of approximately 3 mils (76 micrometers). Obtained. The wet coating was briefly dried at room temperature, followed by complete drying at 100 ° C. for 2 minutes. The coating was then cured at a line speed of 20 fpm using a 500 W Fusion Systems Light Hammer UV chamber purged with dry N2. The coating was exposed to high intensity irradiation of an H bulb.

Preparation of surface modified “fumed” silica for coating formulations CE-4 and EX-6:
(1) Preparation of A-174 modified Cabo-Sperse ™ 1020K:
Available from 1000g Cab-O-Sperse 1020K (20wt% solid fumed silica dispersion, Cabot Corp) in a 3000ml three neck flask equipped with stir bar, stir plate, condenser, heating mantle and thermocouple / temperature controller ) Was loaded. To this dispersion, 1400 g of 1-methoxy-2-propanol was added with stirring. Next, 30.75 g of 97% 3- (methacryloxypropyl) trimethoxysilane (A-174, available from Alfa Aesar (Ward Hill, Mass.)) Was added to a 100 g polybeaker. Propyl) trimethoxysilane was added to the batch with stirring, and a beaker containing 3- (methacryloxypropyl) trimethoxysilane was rinsed with an aliquot of 1-methoxy-2-propanol totaling 100 g. Isopropanol was added to the batch, at which point the batch was an opaque white viscous dispersion, the batch was heated to 80 ° C. and held for about 16 hours, and the resulting mixture was viscous and opaque A white slurry, the batch was cooled to room temperature, vacuum distilled and 900 g 1-methoxy. By performing the addition of 2-propanol alternately, the water was removed from the batch. The batch was concentrated by vacuum distillation, extremely viscous 31.1Wt% solids, yielding an opaque dispersion.

  Preparation of low refractive index coating solution used to make CE-4 and EX-6: First 3.0 g CN9873 (Sartomer, Exton, PA) was dissolved in 7 g ethyl acetate under sonication, 38.6 g (31.1% solids, 12 g solids) of A-174 modified Cabo-Sperse ™ 1020K and 0.23 g of Irgacure 184 are then mixed together to give a resin: particle weight ratio. Coating solution CE-4 was made by forming 1-4 homogeneous coating solution.

  7.4 g UV curable urethane acrylate CN 9893 (Sartomer, Exton, PA) was dissolved in 17.4 g ethyl acetate under sonication and then 95.8 g (31.1% solids, 29. 8 g solid) A-174 modified Cabo-Sperse ™ 1020K, 7.4 g Syloid® RAD 2105 (WR Grace Inc. (Columbia, MD), 2.46 g Tego® RAD 2250 (Silicone acrylate, Evoniks USA (Hopewell, Va.)) And 0.65 g of Irgacure 184 were mixed together under constant stirring for 4 hours to obtain CN 9893: particle ratio 1-4 and diffuser particle content ˜17 wt. By forming a homogeneous solution. To prepare a Ingu solution EX-6.

  Coatings made from solutions CE-4 and EX-6 were made using a UV curable resin mixture. These membranes were dried in an oven at 85 ° C. for 2 minutes and then equipped with an H bulb operating in a nitrogen atmosphere at 100% lamp power, 30 ft / min (9.1 m / min) line speed. Fusion UV-Systems Inc. Cured once using a Light-Hammer 6UV (Gaithersburg, Maryland) processor.

Optical test:
A summary of this example is shown in Table 1. T—H—C refers to transmittance (T), haze (H), and transparency (C). RI is the refractive index. Refractive index (RI) values were determined by using the prism coupling method with a Metricon 2010M prism coupler available from Metricon Corp (Pennington, NJ). RI (n) was determined at 633 nm. The best precision determination of the refractive index of the high haze coating was made by measuring the refractive index of the TM polarization state from the PET surface of the coated film. In this way, the prism and coating PET surfaces were combined and the RI measurement was scanned between n = 1.55 and 1.05. This method results in the detection of two critical angle transitions; one associated with the PET-prism interface at n = ˜1.495 and the other associated with the PET-low index coating interface. Is. The critical angle of this second transition was determined by analyzing the Metricon raw data and using a smoothing analysis program of 200 points above and below the inflection point of this second critical angle. Two linear regions were determined from the smoothed data. The intersection of these two lines corresponded to the inflection point of the curve and hence the RI of the low index coating.

Coated article optics: BYK-Gardner Haze Gard Plus (available from BYK-Gardner USA (Columbia, MD)) was used to determine transmission, haze and transparency values. The reported value represents the average of at least 3 measurements obtained from different areas of the coated film. Transparency value calculations are transmitted light where T ₁ is between 1.6 and ₂ degrees from the normal direction, and T ₂ is between 0 and 0.7 degrees from the normal direction. The ratio (T ₂ −T ₁ ) / (T ₁ + T ₂ ) is used.

  The data in this table indicates that this low index diffuser coating can form optical structures having both high haze and low index properties.

Preparation of two-layer diffusive low-refractive index composition A two-layer diffuser low-refractive index structure was prepared using a sequential coating method. The first layer was composed of a low haze low refractive index layer coated on PET for forming an input substrate S1 for overcoating with a second low refractive index diffuser layer. Substrate S1 was produced by coating a low refractive index coating solution with low haze on a PET film. This solution was made from a mixture of polyvinyl alcohol (PVA) and fumed silica oxide Cab-O-Sperse ™ PG022. In a typical procedure, 5000.0 g Cab-O-Sperse ™ PG 022 dispersion (20 wt% solids) was added to a 20 L plastic container equipped with an air driven laboratory mixer and heating mantle. The silica dispersion was gently stirred and warmed to 45-50 ° C. Once the dispersion has equilibrated in this temperature range, it is available from pre-warmed 90 g of 5 wt% aqueous boric acid (Sigma-Aldrich, Milwaukee, Wis.), 35 g boric acid or 0.035 g boric acid / g equivalent to silica) was added to the silica dispersion and mixed for about 30 minutes. After this time, 100 g of low foaming surfactant (10 wt% Tergitol ™ Min-Foam 1X in water, available from Dow Chemical (Midland, MI)) was added to the silica-boric acid mixture, followed by 168 g of polyvinyl alcohol (PVA) was added. PVA was added as 2315 g of a 7.2 wt% aqueous solution. Upon addition of PVA, the mixture became very viscous and an additional 4350 g DI water was added to reduce the viscosity and ensure proper mixing. The mixture was stirred for an additional 20 minutes under mild conditions. After this time, the coating solution was transferred to a 30 L pressure pot vessel equipped with an air driven stirrer and a vacuum system and degassed at approximately 600-700 mm Hg (80.0-93.3 kPa) for 30-45 minutes. After the mixture was degassed, the solids were checked and found to contain 10.2% solids. The final mixture consisted of 1 part PVA resin: 6 parts silica (1: 6 PVA-Si ratio, 14.3% wt PVA) on a dry weight basis.

  Coating Method: Using a self-rolling knife coating method, the low refractive index coating solution described above is coated on 50 micrometer (2 mil) Dupont-Teijin 689 primer treated PET film to provide a low refractive index coated PET substrate. S1 was produced. The knife was 25.4 cm (10 in) wide and the coating solution was supplied to the coating reservoir by a peristaltic pump. The coating solution was degassed and passed through a nominal 20 micron filter with hydrophilic filtration media available from Meisner Filtration Products (Camarillo, Calif.). In order to prevent solution gelation, the coating solution was delivered to the solution bank while warm while the knife and backup roll were also heated to 38-42 ° C (100.4-107.6 ° F). The knife coating gap ranged from 101.2 micrometers (4 mils). The line speed was 4.57 m / min (15 fpm). The film was dried in a two-zone convection oven with the first zone set at 46.1 ° C. (115 ° F.) and the second zone set at 79.4 ° C. (175 ° F.). The dried coating was approximately 7-8 micrometers thick as measured with a digital micrometer. The refractive index was measured to be 1.164, and the films had 92%, 4% and 100% transmission-haze-transparency (THC) values, respectively.

  Overcoat PET film S1 using a coating solution essentially identical to EX-1 (1-4 PVA-Si + KSR 3A beads) except that the final percent solids of the coating solution is 14.4%. Coated. A second overcoat was applied using the previously described hand coating method. This coating is further described in Table # 2.

  The data in Table # 2 shows that a low refractive index diffuser solution can be coated on different low refractive index layers to make a high haze, low transparency and low refractive index bilayer construction.

  Thus, embodiments of low index diffuser elements are disclosed. These and other implementations are within the scope of the following claims. Those skilled in the art will recognize that the present disclosure can be practiced with embodiments other than those disclosed. The disclosed embodiments are presented for purposes of illustration and not for purposes of limitation, and the present disclosure is limited only by the following claims.

Thus, embodiments of low index diffuser elements are disclosed. These and other implementations are within the scope of the following claims. Those skilled in the art will recognize that the present disclosure can be practiced with embodiments other than those disclosed. The disclosed embodiments are presented for purposes of illustration and not for purposes of limitation, and the present disclosure is limited only by the following claims. A part of the embodiment of the present invention is described in the following items [1]-[37].
[1]
An optical diffuser layer,
A binder,
A plurality of metal oxide particles dispersed in the binder;
A plurality of interconnected air gaps;
A plurality of haze generating particles dispersed in the binder,
An optical diffuser layer, wherein the optical diffuser layer has an effective refractive index of 1.3 or less.
[2]
The optical diffuser layer has an effective refractive index of 1.23 or less when the metal oxide is silica oxide, and 1.33 or less when the metal oxide is alumina oxide. Item 2. The optical diffuser layer according to Item 1, which has an effective refractive index.
[3]
Item 3. The optical diffuser layer of item 1 or 2, wherein the optical diffuser layer has an optical haze of at least 40%.
[4]
Item 3. The optical diffuser layer of item 1 or 2, wherein the optical diffuser layer has an optical haze of at least 60%.
[5]
Item 3. The optical diffuser layer of item 1 or 2, wherein the optical diffuser layer has an optical haze of at least 80%.
[6]
Item 6. The optical diffuser layer according to any one of Items 1 to 5, wherein the haze-generating particles have an average lateral dimension of 1 micrometer or more.
[7]
The optical diffuser layer according to any one of items 1 to 6, wherein the plurality of metal oxide particles include fumed silica or alumina oxide.
[8]
Item 8. The optical diffuser layer according to any one of Items 1 to 7, wherein the optical diffuser layer has a thickness in the range of 1 to 20 micrometers.
[9]
Item 9. The optical diffuser layer according to any one of Items 1 to 8, wherein a volume fraction of the plurality of interconnected voids in the optical diffuser layer is 50% or more.
[10]
The optical diffuser layer according to any one of Items 1 to 9, wherein a weight ratio of the binder to the plurality of metal oxide particles is 1: 1 or less.
[11]
The optical diffuser layer according to any one of Items 1 to 9, wherein a weight ratio of the binder to the plurality of metal oxide particles is 1: 2 or less.
[12]
The optical diffuser layer according to any one of Items 1 to 9, wherein a weight ratio of the binder to the plurality of metal oxide particles is 1: 3 or less.
[13]
Any of items 1-12, wherein the plurality of haze-generating particles have an average lateral dimension in the range of 1 micrometer to 10 micrometers, and the plurality of metal oxide particles comprise fumed metal oxide particles. An optical diffuser layer according to claim 1.
[14]
The plurality of haze-generating particles have an average lateral dimension in the range of 1 micrometer to 10 micrometers, and the plurality of metal oxide particles have an average lateral dimension of 500 nanometers or less. The optical diffuser layer as described in any one of 1-12.
[15]
Item 15. The optical diffuser layer of any of items 1-14, wherein the plurality of haze-generating particles comprise a polymer or inorganic bead having an average lateral dimension in the range of 1 micrometer to 10 micrometers.
[16]
Item 16. The optical diffuser layer according to any one of Items 1 to 15, wherein the optical diffuser layer has an optical transparency of less than 60%.
[17]
The optical diffuser layer according to any one of items 1 to 15, wherein the optical diffuser layer has an optical transparency of less than 15%.
[18]
An optical article,
An optical element;
An optical diffuser layer disposed on the optical element, the optical diffuser layer comprising:
A binder,
A plurality of metal oxide particles dispersed in the binder;
A plurality of interconnected air gaps;
A plurality of haze generating particles dispersed in the binder,
An optical article, wherein the optical diffuser layer has an effective refractive index of 1.3 or less.
[19]
Item 19. The optical article of item 18, wherein the optical diffuser layer has an optical haze of at least 40%.
[20]
Item 20. The optical article according to Item 18 or 19, wherein the optical diffuser layer has an effective refractive index of 1.2 or less.
[21]
21. An optical article according to any one of items 18 to 20, wherein the plurality of haze-generating particles have an average lateral dimension of 1 micrometer or more.
[22]
The optical article according to any one of items 18 to 21, wherein the plurality of metal oxide particles include fumed silica.
[23]
23. Optical article according to any one of items 18-22, wherein the optical diffuser layer has a thickness in the range of 1-20 micrometers.
[24]
24. An optical article according to any one of items 18 to 23, wherein the volume fraction of the plurality of interconnected voids in the optical diffuser layer is 50% or more.
[25]
25. The optical article according to any one of items 18 to 24, wherein a weight ratio of the binder to the plurality of metal oxide particles is 1: 1 or less.
[26]
The optical article according to any one of items 18 to 25, wherein the optical element is a polarizing film, a diffusing film, a reflective film, a retardation film, a light guide, or a liquid crystal display panel.
[27]
A low refractive index layer disposed on the optical element, wherein the optical element separates the optical diffuser layer and the low refractive index layer, and the low refractive index layer has an effective refraction of 1.2 or less. 27. The optical article according to any one of items 18 to 26, having a rate.
[28]
A low refractive index layer disposed on the optical diffuser layer, wherein the optical diffuser layer separates the low refractive index layer and the optical element, and the low refractive index layer is 1.2 or less. 27. The optical article according to any one of items 18 to 26, having an effective refractive index.
[29]
29. An optical article according to any one of items 18 to 28, further comprising an optical adhesive for adhering the optical article to a second optical element.
[30]
Item 30. The optical article according to Item 29, wherein the second optical element is a light guide or a liquid crystal display panel.
[31]
28. The optical article of item 27, wherein the low refractive index layer comprises haze generating particles dispersed in the binder.
[32]
30. The optical article of item 28, wherein the low refractive index layer comprises haze generating particles dispersed in the binder.
[33]
An optical article,
An optical element;
A first low refractive index layer disposed on the optical element, wherein the first low refractive index layer comprises:
A binder,
A plurality of first metal oxide particles having a first average lateral dimension dispersed in the binder;
A plurality of interconnected air gaps;
A plurality of haze generating particles dispersed in the binder,
A first low refractive index layer, wherein the first low refractive index layer has an effective refractive index of 1.3 or less;
A second low refractive index layer disposed on the optical element or the first low refractive index layer, wherein the second low refractive index layer comprises:
A binder,
A plurality of second metal oxide particles dispersed in the binder;
A plurality of interconnected voids, and
An optical article comprising: a second low refractive index layer, wherein the second low refractive index layer has an effective refractive index of 1.3 or less.
[34]
34. An optical article according to item 33, wherein the first low refractive index layer has an optical haze of at least 60%, and the second low refractive index layer has an optical haze of less than 20%.
[35]
The optical article according to item 33 or 34, wherein the optical article has an effective refractive index of 1.23 or less.
[36]
Items 33-35, wherein the second low refractive index layer is disposed on the optical element, and the optical element separates the first low refractive index layer from the second low refractive index layer. The optical article according to any one of the above.
[37]
The second low refractive index layer is disposed on the first low refractive index layer, and the first low refractive index layer separates the second low refractive index layer from the optical element. The optical article according to any one of 33 to 36.

Claims (37)

An optical diffuser layer,
A binder,
A plurality of metal oxide particles dispersed in the binder;
A plurality of interconnected air gaps;
A plurality of haze generating particles dispersed in the binder,
An optical diffuser layer, wherein the optical diffuser layer has an effective refractive index of 1.3 or less.   The optical diffuser layer has an effective refractive index of 1.23 or less when the metal oxide is silica oxide, and 1.33 or less when the metal oxide is alumina oxide. The optical diffuser layer of claim 1 having an effective refractive index.   The optical diffuser layer according to claim 1, wherein the optical diffuser layer has an optical haze of at least 40%.   The optical diffuser layer according to claim 1, wherein the optical diffuser layer has an optical haze of at least 60%.   The optical diffuser layer according to claim 1, wherein the optical diffuser layer has an optical haze of at least 80%.   The optical diffuser layer according to claim 1, wherein the haze-generating particles have an average lateral dimension of 1 micrometer or more.   The optical diffuser layer according to claim 1, wherein the plurality of metal oxide particles include fumed silica or alumina oxide.   The optical diffuser layer according to claim 1, wherein the optical diffuser layer has a thickness in the range of 1 to 20 micrometers.   The optical diffuser layer according to claim 1, wherein a volume fraction of the plurality of interconnected voids in the optical diffuser layer is 50% or more.   The optical diffuser layer according to claim 1, wherein a weight ratio of the binder to the plurality of metal oxide particles is 1: 1 or less.   The optical diffuser layer according to claim 1, wherein a weight ratio of the binder to the plurality of metal oxide particles is 1: 2 or less.   The optical diffuser layer according to claim 1, wherein a weight ratio of the binder to the plurality of metal oxide particles is 1: 3 or less.   The plurality of haze-generating particles have an average lateral dimension in the range of 1 micrometer to 10 micrometers, and the plurality of metal oxide particles comprise fumed metal oxide particles. The optical diffuser layer described.   The plurality of haze-generating particles have an average lateral dimension in the range of 1 micrometer to 10 micrometers, and the plurality of metal oxide particles have an average lateral dimension of 500 nanometers or less. Item 13. An optical diffuser layer according to Item 1-12.   15. The optical diffuser layer of claim 1-14, wherein the plurality of haze generating particles comprise a polymer or inorganic bead having an average lateral dimension in the range of 1 micrometer to 10 micrometers.   The optical diffuser layer according to claim 1, wherein the optical diffuser layer has an optical transparency of less than 60%.   The optical diffuser layer according to claim 1, wherein the optical diffuser layer has an optical transparency of less than 15%. An optical article,
An optical element;
An optical diffuser layer disposed on the optical element, the optical diffuser layer comprising:
A binder,
A plurality of metal oxide particles dispersed in the binder;
A plurality of interconnected air gaps;
A plurality of haze generating particles dispersed in the binder,
An optical article, wherein the optical diffuser layer has an effective refractive index of 1.3 or less.   The optical article of claim 18, wherein the optical diffuser layer has an optical haze of at least 40%.   The optical article according to claim 18, wherein the optical diffuser layer has an effective refractive index of 1.2 or less.   21. The optical article of claim 18-20, wherein the plurality of haze-generating particles have an average lateral dimension of 1 micrometer or greater.   The optical article according to claim 18, wherein the plurality of metal oxide particles include fumed silica.   23. Optical article according to claim 18-22, wherein the optical diffuser layer has a thickness in the range of 1-20 micrometers.   24. The optical article according to claims 18 to 23, wherein the volume fraction of the plurality of interconnected voids in the optical diffuser layer is 50% or more.   25. The optical article according to claim 18 to 24, wherein a weight ratio of the binder to the plurality of metal oxide particles is 1: 1 or less.   The optical article according to claim 18, wherein the optical element is a polarizing film, a diffusion film, a reflection film, a retardation film, a light guide, or a liquid crystal display panel.   A low refractive index layer disposed on the optical element, wherein the optical element separates the optical diffuser layer and the low refractive index layer, and the low refractive index layer has an effective refraction of 1.2 or less. 27. Optical article according to claims 18 to 26, having a rate.   A low refractive index layer disposed on the optical diffuser layer, wherein the optical diffuser layer separates the low refractive index layer and the optical element, and the low refractive index layer is 1.2 or less. 27. Optical article according to claims 18 to 26, having an effective refractive index.   29. The optical article according to claims 18-28, further comprising an optical adhesive that bonds the optical article to a second optical element.   30. The optical article of claim 29, wherein the second optical element is a light guide or a liquid crystal display panel.   28. The optical article of claim 27, wherein the low refractive index layer comprises haze generating particles dispersed in the binder.   30. The optical article of claim 28, wherein the low refractive index layer comprises haze generating particles dispersed in the binder. An optical article,
An optical element;
A first low refractive index layer disposed on the optical element, wherein the first low refractive index layer comprises:
A binder,
A plurality of first metal oxide particles having a first average lateral dimension dispersed in the binder;
A plurality of interconnected air gaps;
A plurality of haze generating particles dispersed in the binder,
A first low refractive index layer, wherein the first low refractive index layer has an effective refractive index of 1.3 or less;
A second low refractive index layer disposed on the optical element or the first low refractive index layer, wherein the second low refractive index layer comprises:
A binder,
A plurality of second metal oxide particles dispersed in the binder;
A plurality of interconnected voids, and
An optical article comprising: a second low refractive index layer, wherein the second low refractive index layer has an effective refractive index of 1.3 or less.   34. The optical article of claim 33, wherein the first low refractive index layer has an optical haze of at least 60% and the second low refractive index layer has an optical haze of less than 20%.   35. The optical article according to claims 33 to 34, wherein the optical article has an effective refractive index of 1.23 or less.   36. The second low refractive index layer is disposed on the optical element, and the optical element separates the first low refractive index layer from the second low refractive index layer. An optical article according to 1.   The second low refractive index layer is disposed on the first low refractive index layer, and the first low refractive index layer separates the second low refractive index layer from the optical element. Item 37. The optical article according to Item 33-36.

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